Method for preparing monolithic coated surfaces

ABSTRACT

A carrier for adsorption a compound, comprising a support; and a shrink-fitted monolithic body attached to and surrounding at least a portion of the support. The monolithic body can be porous and configured to bind compounds in a solution either for the isolation or depletion of the compounds from the solution.

CROSS REFERENCE TO RELATED APPLICATION

This application claims, under 35 U.S.C. § 119(e), the right of priorityto and the benefit of the filing date of co-pending U.S. ProvisionalApplication No. 62/643,658, which was filed on Mar. 15, 2018. Thedisclosure of the foregoing application is incorporated herein byreference in its entirety.

FIELD

The present disclosure generally relates to the field of sampleanalysis, particularly methods and systems method for preparing andusing monolithic coated surfaces.

Introduction

Detection of target compounds in a mixture has numerous applications,from detecting contaminants in our food supply and drinking water,detecting use of banned substances, ensuring medications and dietarysupplements contain the appropriate amount of active ingredients, amongother things. When detecting minute amounts of a compound, such as aheavy metal in a water sample, it may be necessary to concentrate thecompound to aid in detection and quantitation. In other situations,there may be many other compounds in a sample that can interfere withdetection of the target compound, such as testing for residualpesticides in baby food, and separation of the target compound from theinterfering compounds can be necessary.

In order to accomplish the desired detection and quantification, aseries of steps can be performed on a sample to concentrate and/orisolate the target compound. These can include solvent extractions,concentrating or drying a sample, centrifugation to remove solidparticulates, and the like. Performing a series of steps to prepare fordetecting the target compound can be time consuming and lead to errors.

U.S. Pat. No. 6,197,597 describes a separating agent, such as anantibody, bound to the surface of a solid body for the purpose ofperforming an immunoassay. However, many compounds are not suitable fordetection by immunoassay as they may be too small to bind specificallyto an antibody or an appropriate antibody may not be known.

U.S. Pat. No. 5,691,206 describes a coated fiber for solid phaseextraction. While the fiber has the ability to bind a target compound,the capacity of the fiber is limited by the thin coating of material onthe fiber.

As such, there is a need for tools and methods to simplify samplepreparation and aid in the accurate detection and quantification oftarget compounds in a more efficient manner.

SUMMARY

In a first aspect, a carrier for adsorption a compound can include asupport and a shrink-fitted monolithic body attached to and surroundingat least a portion of the support.

In various embodiments of the first aspect, the shrink-fitted monolithicbody can be porous.

In various embodiments of the first aspect, the support is a rod.

In various embodiments of the first aspect, the support is a magnet orpolymer coated magnet.

In various embodiments of the first aspect, the shrink-fitted monolithicbody can have an average thickness of not less than about 0.5millimeters, such as not less than about 0.75 mm, even not less thanabout 1.0 millimeters. In particular embodiments, the shrink-fittedmonolithic body can have an average thickness of not greater than about100 millimeters.

In a second aspect, a system for testing a sample for the presence of acompound can include a carrier and a container. The carrier can includea support and a shrink-fitted monolithic body attached to andsurrounding at least a portion of the support. The container can includea cavity for holding a sample. The shrink-fitted monolithic body sizedto fit within the cavity and to be in contact with the sample.

In various embodiments of the second aspect, the support can be a rod.

In various embodiments of the second aspect, the support can be a magnetor polymer coated magnet.

In various embodiments of the second aspect, the shrink-fittedmonolithic body can have an average thickness of not less than about 0.5millimeters, such as not less than about 0.75 mm, even not less thanabout 1.0 millimeter. In particular embodiments, the shrink-fittedmonolithic body can have an average thickness of not greater than about100 millimeters.

In various embodiments of the second aspect, the shrink-fittedmonolithic body can conform to the shape of the cavity.

In a third aspect, a method for producing a carrier can includepositioning a support within a cavity; filing the cavity with asolution, the solution including a monomer and an initiator mixture;applying energy to the solution to cause polymerization of the monomerto form a monolith, wherein monolith shrinks during polymerization andcuring and the shrinkage adheres the monolith to the support; andremoving the support with the attached monolith.

In various embodiments of the third aspect, the positioning can includecentering the support within the cavity.

In various embodiments of the third aspect, the solution further caninclude a porogen.

In various embodiments of the third aspect, the energy can includethermal energy or electromagnetic energy.

In various embodiments of the third aspect, the support can be a rod.

In various embodiments of the third aspect, the support can be a magnetor polymer coated magnet.

In various embodiments of the third aspect, the shrink-fitted monolithicbody can have an average thickness of not less than about 0.5millimeters, such as not less than about 0.75 mm, even not less thanabout 1.0 millimeter. In particular embodiments, the shrink-fittedmonolithic body can have an average thickness of not greater than about100 millimeters.

In various embodiments of the third aspect, the shrink-fitted monolithicbody can conform to the shape of the cavity.

In a fourth aspect, a method of determining the presence of a compoundin a solution can include adding the solution to a container, andinserting a carrier into the container. The carrier can include asupport and a shrink-fitted monolith adhered to the substrate. Theshrink-fitted monolith can be in contact with the solution. In variousembodiments, the method can include adsorbing the compound to theshrink-fitted monolith; removing the shrink-fitted monolith from thesolution in the container; providing the compound to a detector; anddetecting and/or quantifying the amount of the compound in the solutionbased on an output of the detector. Alternatively, the method caninclude adsorbing interfering compounds to the shrink-fitted monolith;removing the shrink-fitted monolith from the solution in the container;providing the solution to the detector; and detecting and/or quantifyingthe amount of the compound in the solution based on an output of thedetector.

In various embodiments of the fourth aspect, the substrate can be a rod.

In various embodiments of the fourth aspect, the substrate can be amagnet or polymer coated magnet.

In various embodiments of the fourth aspect, the shrink-fittedmonolithic body can have an average thickness of not less than about 0.5millimeters, such as not less than about 0.75 mm, even not less thanabout 1.0 millimeter. In particular embodiments, the shrink-fittedmonolithic body can have an average thickness of not greater than about100 millimeters.

In various embodiments of the fourth aspect, the shrink-fittedmonolithic body can conform to the shape of the container.

In various embodiments of the fourth aspect, the detector can include amass spectrometer.

In various embodiments of the fourth aspect, the detector can include aliquid chromatography system. In particular embodiments, the liquidchromatography system can include an optical detector, a flameionization detector, or any combination thereof. In particularembodiments, the optical detector can include a UV detector, an IRdetector, a visible light detector, a Raman detector, or any combinationthereof.

In various embodiments of the fourth aspect, the detector can include ascintillation counter, an X-ray fluorescence detector, or anycombination thereof.

In various embodiments of the fourth aspect, the detector can include acharged aerosol detector, a flame ionization detector, an aerosol-baseddetector, a flame photometric detector, an atomic-emission detector, anitrogen phosphorus detector, an evaporative light scattering detector,an electrolytic conductivity detector, a MIRA detector, or anycombination thereof.

In various embodiments of the fourth aspect, providing the compound tothe detector can include removing the compound from the shrink-fittedmonolith to the detector. In particular embodiments, removing thecompound from the shrink-fitted monolith to the detector can includeeluting the compound into a solution and providing the solution to thedetector.

In various embodiments of the fourth aspect, providing the compound tothe detector can include providing the carrier and the adhered compoundto the detector.

In various embodiments of the fourth aspect, providing the compound tothe detector can include transferring the adhered compound from thecarrier into the detector.

DRAWINGS

For a more complete understanding of the principles disclosed herein,and the advantages thereof, reference is now made to the followingdescriptions taken in conjunction with the accompanying drawings andexhibits, in which:

FIG. 1 is a flow diagram illustrating an exemplary method formanufacturing carriers, in accordance with various embodiments.

FIG. 2 is a cross section of a carrier along the length of the supportillustrating various monolith shapes, in accordance with variousembodiments.

FIG. 3A is a cross section of a carrier along the length of the supportillustrating various support structures, in accordance with variousembodiments.

FIG. 3B is a cross section of a carrier illustrating a fullyencapsulated support, in accordance with various embodiments.

FIG. 4 is a cross section of a carrier perpendicular to the length ofthe support illustrating various support cross sections, in accordancewith various embodiments.

FIGS. 5 and 6 are flow diagrams illustrating exemplary methods fordetecting and/or quantifying compounds in a sample, in accordance withvarious embodiments.

FIG. 7 is a diagram illustrating the carrier in use with a samplecontainer, in accordance with various embodiments.

FIG. 8 is a scanning electron micrograph of 2:1 n-heptane-DVB monolithat 47 μm full scale, in accordance with various embodiments.

FIG. 9 is a scanning electron micrograph of 2:1 THF-DVB monolith at 47μm full scale, in accordance with various embodiments.

FIG. 10 is a scanning electron micrograph of 1.5:1 n-heptane-DVB/VPmonolith at 60 μm full scale, in accordance with various embodiments.

FIG. 11 shows the adsorption efficiency of a DVB/n-heptane porousmonolith carrier for alkylphenones, in accordance with variousembodiments.

FIG. 12 shows the adsorption efficiency of a DVB/n-heptane and DVB/DMFporous monolith carriers for caffeine, in accordance with variousembodiments.

FIG. 13 shows the adsorption efficiency of organochloro pesticides on aDVB/n-heptane porous monolith, in accordance with various embodiments.

FIG. 14 shows the desorption efficiency of organochloro pesticides froma DVB/n-heptane porous monolith, in accordance with various embodiments.

It is to be understood that the figures are not necessarily drawn toscale, nor are the objects in the figures necessarily drawn to scale inrelationship to one another. The figures are depictions that areintended to bring clarity and understanding to various embodiments ofapparatuses, systems, and methods disclosed herein. Wherever possible,the same reference numbers will be used throughout the drawings to referto the same or like parts. Moreover, it should be appreciated that thedrawings are not intended to limit the scope of the present teachings inany way.

DESCRIPTION OF VARIOUS EMBODIMENTS

Embodiments of systems and methods for analyteisolation are describedherein and in the accompanying exhibits.

The section headings used herein are for organizational purposes onlyand are not to be construed as limiting the described subject matter inany way.

In this detailed description of the various embodiments, for purposes ofexplanation, numerous specific details are set forth to provide athorough understanding of the embodiments disclosed. One skilled in theart will appreciate, however, that these various embodiments may bepracticed with or without these specific details. In other instances,structures and devices are shown in block diagram form. Furthermore, oneskilled in the art can readily appreciate that the specific sequences inwhich methods are presented and performed are illustrative and it iscontemplated that the sequences can be varied and still remain withinthe spirit and scope of the various embodiments disclosed herein.

All literature and similar materials cited in this application,including but not limited to, patents, patent applications, articles,books, treatises, and internet web pages are expressly incorporated byreference in their entirety for any purpose. Unless described otherwise,all technical and scientific terms used herein have a meaning as iscommonly understood by one of ordinary skill in the art to which thevarious embodiments described herein belongs.

It will be appreciated that there is an implied “about” prior to thetemperatures, concentrations, times, pressures, flow rates,cross-sectional areas, etc. discussed in the present teachings, suchthat slight and insubstantial deviations are within the scope of thepresent teachings. In this application, the use of the singular includesthe plural unless specifically stated otherwise. Also, the use of“comprise”, “comprises”, “comprising”, “contain”, “contains”,“containing”, “include”, “includes”, and “including” are not intended tobe limiting. It is to be understood that both the foregoing generaldescription and the following detailed description are exemplary andexplanatory only and are not restrictive of the present teachings.

As used herein, “a” or “an” also may refer to “at least one” or “one ormore.” Also, the use of “or” is inclusive, such that the phrase “A or B”is true when “A” is true, “B” is true, or both “A” and “B” are true.Further, unless otherwise required by context, singular terms shallinclude pluralities and plural terms shall include the singular.

A “system” sets forth a set of components, real or abstract, comprisinga whole where each component interacts with or is related to at leastone other component within the whole.

FIG. 1 is a flow diagram illustrating a method 100 of forming a carrier.At 102, a support can be placed within a cavity, and, at 104, the cavitycan be filled with a solution. In various embodiments, the cavity can befilled with the solution prior to placement of the support. In variousembodiments, the support can be a rod or similar shaped supportstructure that extends from the carrier. In various embodiments, thesupport can be made of a polymer, polymer coated metal, a magnet, apolymer coated magnet, or the like. In various embodiments, the polymercan include a thermoplastic such as polyether ether ketone (PEEK),poly(methyl methacrylate) (PMMA), polyamide, polycarbonate,polyethylene, polyvinyl chloride, polyphenylene oxide, polyphenylenesulfide, polypropylene, polytetrafluoroethylene (PTFE), and the like. Invarious embodiments, the support or at least a coating on the surface ofthe support can be inert to prevent reactions with the polymer, themonomer solution or the sample solution.

In various embodiments, the solution can include a monomer and aninitiator. In various embodiments, the monomer, for example, can bedivinylbenzene. In various embodiments, the initiator can be a freeradical initiator, such as azobisisobutyronitrile. In particularembodiments, the solution can also include a porogen. Various otherchemistries that are adaptable for use in the formation of theshrink-fitted monolith are known in the art, such as, for exampleEuropean Patent 1,188,736 which describes a method of making porouspoly(ethylene glycol methacrylate-co-ethylene glycol dimethacrylate) byin situ copolymerization of a monomer, a crosslinking agent, a porogenicsolvent and an initiator, U.S. Pat. Nos. 5,334,310; 5,453,185 and5,728,457 which disclose methods of making macroporous poly(glycidylmethacrylate-co-ethylene glycol dimethacrylate) polystyrene, and U.S.Pat. No. 7,473,367 which discloses permeable polymeric monolithicmaterials prepared in a plastic column casing, all of which areincorporated by reference for all purposes.

At 106, energy can be applied to the solution to trigger polymerizationto form a monolith. In various embodiments, the energy can be UV orvisible light, X-rays, gamma rays, or other types of radiation. Forexample, a UV initiated process for producing monoliths is disclosed inFlook, K., Agroskin, Y., Pohl, C., Reversed-phase monoliths prepared byUV polymerization of divinylbenzene. Journal of Separation Science 2011;34(16-17): p. 2047-2053 and U.S. Pat. Appl. No. 2010/0038298 A1discloses preparing monolithic columns with a gamma radiation-inducedpolymerization process. In other embodiments, thermal energy can beapplied to induce polymerization. For example, U.S. Pat. No. 7,473,367which discloses preparing monolithic columns using a thermalpolymerization process. The energy applied and the time can becontrolled to achieve the desired degree of polymerization. In variousembodiments, during polymerization and curing of the monolith, thepolymer can shrink, thereby releasing from the cavity and adhering tothe support.

In other embodiments, the support can be a disk or other shape that canbe fully encapsulated within the carrier. The support can be suspendedwithin the cavity so as to not contact the cavity walls, such as byusing magnetic levitation or solution viscosity to prevent settling ofthe support during polymerization. Alternatively, the support can beplaced within the filled cavity and the cavity can be rapidly rotated ortumbled to keep the support centered within the cavity duringpolymerization.

At 108, the carrier, including the support and the attachedshrink-fitted monolith, can be removed from the cavity. In variousembodiments, the monolithic porous polymer can have a surface area in arange of about 20 m²/g to about 900 m²/g.

In various embodiments the monolith can take on the shape of the cavity.FIG. 2 illustrates various cross-sectional shapes. Cross section 202illustrates a monolith with a rectangular cross section, such as acylinder, where the side surfaces are parallel and the bottom surface isflat. Cross section 204 illustrates a trapezoidal cross section wherethe side surfaces are tapered. Cross section 204 retains the flat bottomof cross section 202.

Cross section 206 illustrates a higher order polygonal cross sectionwhere the greatest width is in the middle with a narrower top andbottom. Cross section 206 can be produced with a two part cavity suchthat the cavity can be separated for removal of the monolith. Crosssection 206 also retains the flat bottom of cross section 202 and 204.

Cross section 208 illustrates a triangular cross section where sidestaper to a point at the bottom.

In various embodiments, cross-sections 202, 204, and 206 can be modifiedsuch that the bottom surface is curved with either a concave of convexcurvature. Additionally, the side surfaces can be curved with either aconcave of convex curvature.

FIG. 3 illustrates various end treatments of the support. In variousembodiments, such as cross section 302 where the support has arectangular cross section, the monolith can be held onto the support bythe adhesion from the shrinkage of the monolith during curing. In otherembodiments, such as cross sections 304, 306, and 308, the end of thesupport can be modified to reduce the likelihood the support can bewithdrawn from the monolith. For example, in cross section 304, the endportion of the support can be widened with a larger rectangular portion.In various embodiments, the widened rectangular portion can representvarious enlargements such as a rectangular or triangular prism or anenlarged cylinder located at the support end. In other embodiments, theend portion can be flattened in one dimension orthogonal to the lengthof the support to widen the support in a second orthogonal dimension.

Cross section 306 shows a triangular end modification. The triangularcross section can represent a pyramidal modification or a conicalmodification of the support end. Cross section 308 shows a circular endmodification, such as a ball or disc at the end of the support.

In other embodiments, the end portion can be modified to form othershapes as would be obvious to one skilled in the art and still withinthe scope of this disclosure.

Because the monolith is formed in the presence of the support, narrowerspace for the upper portion of the support can substantially prevent thewithdrawal of the end portion with the larger or differently shapedcross section.

FIG. 3B illustrates an exemplary carrier 320 in which a support 322 isfully encapsulated with monolith 324. Rather than holding the support bya portion sticking out of the carrier, carrier 320 can be formed bysuspending support 322 within the polymerization while forming themonolith. For example, support 322 can be a magnet, or polymer coatedmagnet, and can be suspending using magnetic levitation duringpolymerization of the monolith. While support 322 is illustrated as anovoid or disc, various alternative shapes, including cylinders,pyramids, cuboids, other convex and concave polyhedrons, and the likecan provide suitable supports for embedding within the monolith.

FIG. 4 illustrates various support shapes, represented by cross sectionsperpendicular to the length of the support. Cross section 402illustrates a support with a circular cross section, such as a cylinder.Cross sections 404, 406, and 408 illustrate alternatives to acylindrical rod, such as a square rod (cross section 404), a triangularrod (cross section 406), and a rectangular rod (cross section 408).

FIG. 4 also illustrated the thickness of the monolith. The overall width410 of the monolith can be measured from one outer surface to anopposite outer surface. The thickness 412 of the monolith can bemeasured from the outer surface of the support to the outer surface ofthe monolith. In various embodiments, the thickness 412 of the monolithcan be not less than about 0.5 millimeters, such as not less than about0.75 millimeters, such as not less than about 1.0 millimeters.Additionally, the thickness 412 may be not greater than about 100millimeters, such as not greater than about 50 millimeters, even notgreater than about 25 millimeters. Generally, if the thickness 412 ofthe monolith is too small, there will be insufficient adhesion betweenthe support and the monolith as the degree of shrinkage is dependent onthe thickness of the monolith.

Generally, the overall width of the monolith can be between about 1.0millimeter to about 300 millimeters, such as between about 1.5millimeters to about 200 millimeters, even between about 2.0 millimetersand about 75 millimeters.

In various embodiments, the ratio of the thickness of the monolith tothe diameter of the support can be in a range of about 1:2 to about50:1, such as between about 1:1 to about 25:1, even between about 2:1 toabout 10:1.

There can be a relationship between the size of the monolith and theadsorption capacity of the carrier, with a larger monolith having agreater capacity to adsorb a target compound. However, as the thicknessof the monolith increases, the time to equilibrate with the solution(diffusion of the compound through the monolith) increases, as does thetime to extract or elute the compound from the monolith. In variousembodiments, for large monoliths, increasing the diameter of the support414 while maintaining the same thickness 412 of the monolith canincrease the capacity of the monolith while minimizing changes to theequilibration time. However, maintaining the support diameter 414 whileincreasing the monolith thickness 412 can provide a greater increase incapacity for a given monolith width 410 at the cost of equilibrationtime.

FIG. 5 illustrates an exemplary use case for the carrier. At 502, asample solution can be added to a container. In various embodiments, thesample solution can contain a compound of interest as well as additionalcompounds that may interfere with the detection of compound of interestin the sample.

At 504, a carrier can be inserted into the solution within thecontainer. FIG. 7 illustrates carrier 702 and solution 704 within thecontainer 706. In various embodiments, the shape of the monolith 708 ofthe carrier 702 can conform to the shape of the container 706, therebymaximize the size of the monolith 708 for a given container 706.Alternatively, the monolith 708 shape may be different than thecontainer 706 shape. Other shapes may improve the amount of surface areain contact with the solution. Other monolith shape and container shapecombinations may improve other aspects, such as sample volume. Stillfurther, the monolith 708 can have a generic shape for use with avariety of containers 706.

Returning to FIG. 5, at 506, the target compound can be adsorbed to thecarrier. In various embodiments, the carrier may be moved within thecontainer to mix the solution and decrease the time required for thecompound to adsorb to the carrier. For example, the carrier may berotated or be translated up and down or side to side to agitate thesolution.

At 508, the carrier can be removed from the solution. Optionally, at510, the carrier may be washed to remove any remaining solution as wellas interfering compounds from the surface of the carrier. In variousembodiments, washing the carrier can include dipping the monolithportion of the carrier into a wash solution. Preferably, the washsolution does not cause desorption of the target compound. Additionally,the carrier may be moved to agitate the wash solution.

Optionally, at 512, the target compound can be eluted from the carrier.In various embodiments, the carrier can be inserted into an elutionsolution that causes desorption of the target compound. The carrier maybe moved within the elution solution to aid in desorption.

At 514, the compound can be detected and/or quantified. In variousembodiments, the elution solution can be provided to a detector and ameasurement of the target compound in the solution can be obtained. Forexample, the elution solution can be provided to a chromatographysystem, such as a liquid chromatography or gas chromatography system andthe target compound can be measured after chromatographic separation.Alternatively, the elution solution can be provided directly to thedetector without chromatographic separation.

Alternatively, the carrier can be provided to the detector for ameasurement of the compound on the carrier without elution of thecompound into a solution. For example, the target compound can bemeasured while adsorbed on the carrier. Alternatively, the targetcompound can be directly desorbed from the carrier to the detector, forexample by applying an electric current, heat, a vacuum, or acombination thereof.

In various embodiments, the detector can be an optical detector, such asa UV/VIS detector, an IR detector, or a Raman detector, a flameionization detector, flame photometric detector, a charged aerosoldetector, aerosol-based detector, atomic-emission detector, nitrogenphosphorus detector, evaporative light scattering detector, a massspectrometer, an electrolytic conductivity detector, MIRA detector, anX-ray fluorescence detector, a scintillation counter, or the like.

FIG. 6 illustrates another exemplary use case for the carrier. At 602, asample solution can be added to a container. In various embodiments, thesample solution can contain a compound of interest as well as additionalcompounds that may interfere with the detection of compound of interestin the sample.

At 604, a carrier can be inserted into the solution within thecontainer. At 606, interfering compounds can be adsorbed to the carrier.In various embodiments, the carrier may be moved within the container tomix the solution and decrease the time required for the interferingcompound to adsorb to the carrier. For example, the carrier may berotated or be translated up and down or side to side to agitate thesolution.

At 608, the carrier can be removed from the solution, and 614, thecompound can be detected and/or quantified. In various embodiments, thesolution can be provided to a detector and a measurement of the targetcompound in the solution can be obtained.

While the present teachings are described in conjunction with variousembodiments, it is not intended that the present teachings be limited tosuch embodiments. On the contrary, the present teachings encompassvarious alternatives, modifications, and equivalents, as will beappreciated by those of skill in the art.

Further, in describing various embodiments, the specification may havepresented a method and/or process as a particular sequence of steps.However, to the extent that the method or process does not rely on theparticular order of steps set forth herein, the method or process shouldnot be limited to the particular sequence of steps described. As one ofordinary skill in the art would appreciate, other sequences of steps maybe possible. Therefore, the particular order of the steps set forth inthe specification should not be construed as limitations on the claims.In addition, the claims directed to the method and/or process should notbe limited to the performance of their steps in the order written, andone skilled in the art can readily appreciate that the sequences may bevaried and still remain within the spirit and scope of the variousembodiments.

The embodiments described herein, can be practiced with other computersystem configurations including hand-held devices, microprocessorsystems, microprocessor-based or programmable consumer electronics,minicomputers, mainframe computers and the like. The embodiments canalso be practiced in distributing computing environments where tasks areperformed by remote processing devices that are linked through anetwork.

It should also be understood that the embodiments described herein canemploy various computer-implemented operations involving data stored incomputer systems. These operations are those requiring physicalmanipulation of physical quantities. Usually, though not necessarily,these quantities take the form of electrical or magnetic signals capableof being stored, transferred, combined, compared, and otherwisemanipulated. Further, the manipulations performed are often referred toin terms, such as producing, identifying, determining, or comparing.

Any of the operations that form part of the embodiments described hereinare useful machine operations. The embodiments, described herein, alsorelate to a device or an apparatus for performing these operations. Thesystems and methods described herein can be specially constructed forthe required purposes or it may be a general purpose computerselectively activated or configured by a computer program stored in thecomputer. In particular, various general purpose machines may be usedwith computer programs written in accordance with the teachings herein,or it may be more convenient to construct a more specialized apparatusto perform the required operations.

Certain embodiments can also be embodied as computer readable code on acomputer readable medium. The computer readable medium is any datastorage device that can store data, which can thereafter be read by acomputer system. Examples of the computer readable medium include harddrives, network attached storage (NAS), read-only memory, random-accessmemory, CD-ROMs, CD-Rs, CD-RWs, magnetic tapes, and other optical andnon-optical data storage devices. The computer readable medium can alsobe distributed over a network coupled computer systems so that thecomputer readable code is stored and executed in a distributed fashion.

EXAMPLES Example 1A. Preparation of a Hydrophobic Monolith Carrier witha Non-Polar Porogen

A polytetrafluoroethylene (PTFE) machined mold with a cavity dimensionof 4.7 mm diameter and 38 mm in length is used with a 1.6 mm×89 mmpolyetheretherketone (PEEK) carrier rod. The rod is geometricallydeformed at one end by heating the PEEK to around the glass transitiontemperature of approximately 140° C. and then mechanically pressing theheated portion of the rod. The mechanically pressed portion is deformedto widen and flatten the rod and to emboss the rod with one or moregroves to aid in anchoring the monolith. The support rod is placed intothe cavity. A threaded fitting at the inlet of the PTFE machined moldcenters the support rod in the cavity and also seals the cavity.

A solution consisting of technical grade divinylbenzene monomer (DVB,designated 55% pure and contained a polymerization inhibitor), n-heptaneand a radical initiator, azobisisobutyronitrile (AIBN) is prepared. Theporogen, n-heptane, is non-polar and is readily miscible with the DVBmonomer. The n-heptane porogen is added at twice the mass of the DVBmonomer. The AIBN initiator is added at approximately 1% of the DVBmass. The monomer-porogen-initiator (MPI) solution is then added to thecavity (0.4 mL), the support rod is inserted and the threaded fitting isattached to seal the cavity.

The PTFE mold containing the MPI solution and support rod is placed inan oven at 65° C. for 24-48 hours to initiate the polymerization. Afterpolymerization, the threaded fitting is removed and the support rod isextracted from the mold. As a result of the shrinking of the porousmonolith during polymerization, the monolith is securely attached to thesupport rod. The thickness of the resulting porous monolith is 1.5 mm.FIG. 8 shows a scanning electron micrograph (SEM) of the resultingporous monolith.

Example 1B. Preparation of a Hydrophobic Monolith Carrier with a PolarPorogen

A polytetrafluoroethylene (PTFE) machined mold with a cavity dimensionof 4.7 mm diameter and 38 mm in length is used with a 1.6 mm×89 mmpolyetheretherketone (PEEK) carrier rod. The rod is geometricallydeformed at one end by heating the PEEK to around the glass transitiontemperature of approximately 140° C. and then mechanically pressing theheated portion of the rod. The mechanically pressed portion is deformedto widen and flatten the rod and to emboss the rod with one or moregroves to aid in anchoring the monolith. The support rod is placed intothe cavity. A threaded fitting at the inlet of the PTFE machined moldcenters the support rod in the cavity and also seals the cavity.

A solution consisting of technical grade divinylbenzene monomer (DVB,designated 55% pure and contained a polymerization inhibitor),dimethylformamide (DMF) and a radical initiator, azobisisobutyronitrile(AIBN) is prepared. The porogen, DMF, is slightly polar and is misciblewith the DVB monomer. The DMF porogen is added at twice the mass of theDVB monomer. The AIBN initiator is added at approximately 1% of the DVBmass. The monomer-porogen-initiator (MPI) solution is then added to thecavity (0.4 mL), the support rod is inserted and the threaded fitting isattached to seal the cavity.

The PTFE mold containing the MPI solution and support rod is placed inan oven at 65° C. for 24-48 hours to initiate the polymerization. Afterpolymerization, the threaded fitting is removed and the support rod isextracted from the mold. As a result of the shrinking of the porousmonolith during polymerization, the monolith is securely attached to thesupport rod. The thickness of the resulting porous monolith is 1.5 mm.DMF produces smaller pores than n-heptane when used with DVB.

Example 2. Preparation of a Hydrophobic Monolith Carrier with aModerately Polar Porogen

A polytetrafluoroethylene (PTFE) machined mold with a cavity dimensionof 4.7 mm diameter and 38 mm in length is used with a 1.6 mm×89 mmpolyetheretherketone (PEEK) carrier rod. The rod is geometricallydeformed at one end by heating the PEEK to around the glass transitiontemperature of approximately 140° C. and then mechanically pressing theheated portion of the rod. The mechanically pressed portion is deformedto widen and flatten the rod and to emboss the rod with one or moregroves to aid in anchoring the monolith. The support rod is placed intothe cavity. A threaded fitting at the inlet of the PTFE machined moldcenters the support rod in the cavity and also seals the cavity.

A solution consisting of technical grade divinylbenzene monomer (DVB,designated 55% pure and contained a polymerization inhibitor),tetrahydrofuran (THF) and a radical initiator, azobisisobutyronitrile(AIBN) is prepared. The porogen, THF exhibits moderately polarity and ismiscible with the DVB monomer. The THF porogen is added at twice themass of the DVB monomer. The AIBN initiator is added at approximately 1%of the DVB mass. The monomer-porogen-initiator (MPI) solution is thenadded to the cavity (0.4 mL), the support rod is inserted and thethreaded fitting attached to seal the cavity.

The PTFE mold containing the MPI solution and support rod is placed inan oven at 65° C. for 24-48 hours to initiate the polymerization. Afterpolymerization, the threaded fitting is removed and the support rod isextracted from the mold. As a result of the shrinking of the porousmonolith during polymerization, the monolith is securely attached to thesupport rod. The thickness of the porous monolith is 1.5 mm. FIG. 9shows a scanning electron micrograph (SEM) of the resulting porousmonolith.

Example 3. Preparation of a Copolymer Porous Monolith with a Non-PolarPorogen

In examples 1 and 2, a carrier composed of a DVB porous polymer isdescribed. In this example, a carrier with a porous copolymer consistingof two monomers, divinylbenzene and n-vinylpyrrolidone is described.

A polytetrafluoroethylene (PTFE) machined mold with a cavity dimensionof 3.2 mm diameter and 38 mm in length is used with a 1.6 mm×89 mmpolyetheretherketone (PEEK) carrier rod. The rod is geometricallydeformed at one end by heating the PEEK to around the glass transitiontemperature of approximately 140° C. and then mechanically pressing theheated portion of the rod. The mechanically pressed portion is deformedto widen and flatten the rod and to emboss the rod with one or moregroves to aid in anchoring the monolith. The support rod is placed intothe cavity. A threaded fitting at the inlet of the PTFE machined moldcenters the support rod in the cavity and also seals the cavity.

A solution consisting of technical grade divinylbenzene monomer (DVB,designated 55% pure and contained a polymerization inhibitor),n-vinylpyrrolidone monomer (VP), n-heptane as a porogen and a radicalinitiator, azobisisobutyronitrile (AIBN) is prepared. The mass ratio ofDVB to VP is 5:1 (80% DVB and 20% VP). The mass ratio of the porogen,n-heptane to the total mass of the DVB and VP monomer solution is 2:1.The AIBN initiator is added at approximately 1%-2% of the total monomermass. The monomer-porogen-initiator (MPI) solution is then added to thecavity (0.5 mL), the support rod is inserted and the threaded fitting isattached to seal the cavity.

The PTFE mold containing the MPI solution and support rod is placed inan oven at 65° C. for 24-48 hours to initiate the polymerization. Afterpolymerization, the threaded fitting is removed and the support rodextracted from the mold. As a result of the shrinking of the porousmonolith during polymerization, the monolith is securely attached to thesupport rod. The thickness of the resulting porous monolith isapproximately 0.80 mm. FIG. 10 shows a scanning electron micrograph(SEM) of the resulting porous monolith.

Example 4. Extraction of Aromatic Analytes Using a Porous MonolithCarrier

A carrier of Example 1A is cleaned with acetone in an ultrasonic bath (3acetone rinses, 5 minutes each in the ultrasonic bath) to removeresidual porogen, oligomers, inhibitor or initiator from the porousmonolith. The carrier is then dried in a 50° C. oven for ten minutes.

A test solution of 5% methanol in water containing 10 μg/mL of threealkylphenones (acetophenone, propriophenone and butyrophenone) is usedfor evaluating the adsorption efficiency of the carrier of example 1.Reversed phase HPLC with UV detection is used to monitor the timedependent adsorption of the alkyphenones onto the carrier from the testsolution. Prior to inserting the carrier into the test solution, thecarrier is inserted into a 50% methanol/water solution to “wet” thesurface of the hydrophobic porous monolith. After inserting the carrierinto the test solution for 3 minutes, the carrier is removed and HPLCanalysis used determine the concentration of the remaining alkyphenones.This process is repeated every three minutes up to fifteen minutes andthe data shown in FIG. 11. This data show that aromatic, hydrophobicanalytes are effectively retained on this type of carrier.

Example 5. Extraction of Caffeine from Coffee Using a Porous MonolithCarrier

Caffeine is an important indicator for the anthropogenic contaminationof natural waters and its presence closely parallels more toxiccontaminants such as fecal coliforms. Caffeine is relatively watersoluble, hence a challenging molecule for retention on a hydrophobiccarrier. Two carriers are tested for their ability to retain caffeine.The first carrier consists of a DVB/n-heptane porous monolith asdescribed in Example 1A. The second carrier is a porous DVB monolithusing dimethylformamide (DMF) as the porogen as described in Example 1B.After synthesis, both carriers are cleaned with acetone in an ultrasonicbath (3 acetone rinses, 5 minutes each in the ultrasonic bath) to removeresidual porogen, oligomers, inhibitor or initiator from the porousmonoliths. The carriers are then dried in a 50° C. oven for ten minutes.

A sample containing 100 ppm caffeine (in 5% methanol) is prepared. TheDVB/n-heptane carrier (53 mg monolith not including the mass of thesupport) is placed in 5 mL of the caffeine solution and gently agitatedand removed after three minutes. The remaining caffeine in the solutionis then determined by HPLC and this process is repeated at 6, 9 and 12minutes. The same procedure is followed for the DVB/DMF carrier (67 mgmonolith not including the mass of the support). FIG. 12 shows the %adsorption of caffeine as a function of time.

Example 6. Adsorption and Desorption of Organochlorine Pesticides andRelated Compounds

A test solution containing nitrobenzene (1 ppm), 1-chloro-4-nitrobenzene(1 ppm), 1,4-dichlorobenzene (1 ppm), methoxychlor (1 ppm),pentachloronitrobenzene (1 ppm), 4,4′-DDT (2.5 ppm) andhexachlorobenzene (2.5 ppm) in 50% acetonitrile is prepared. A carrierconsisting of a DVB/n-heptane porous monolith of (81 mg monolith notincluding the mass of the support) is immersed into 5 mL of the testsolution and is ultrasonicated for one minute. After one minute, thecarrier is removed and the remaining analytes in the test solution aredetermined by HPLC. This process is repeated four more times and eachtime the remaining analytes are determined by HPLC. The results areshown in FIG. 13. Notably, the more hydrophobic the analyte, the greaterthe retention on the hydrophobic carrier.

The carrier with the adsorbed analytes is immersed into 5 mL ofacetonitrile for five minutes to desorb the analytes. The solution isthen analyzed by HPLC. The process is repeated at fifteen and thirtyminutes. As shown in FIG. 14, the less hydrophobic analytes are moreefficiently removed from the carrier. By using a more hydrophobicsolvent such as THF, removal efficiency of the analytes from the carriercan be improved.

1. A carrier for adsorption a compound, comprising: a support; and ashrink-fitted monolithic body attached to and surrounding at least aportion of the support.
 2. The carrier of claim 1 wherein theshrink-fitted monolithic body is porous.
 3. The carrier of claim 1wherein the support is a rod.
 4. The carrier of claim 1 wherein thesupport is a magnet or polymer coated magnet.
 5. The carrier of claim 1wherein the shrink-fitted monolithic body has an average thickness ofnot less than about 0.5 millimeters.
 6. The carrier of claim 5 whereinthe shrink-fitted monolithic body has an average thickness of not lessthan about 0.75 mm.
 7. The carrier of claim 6 wherein the shrink-fittedmonolithic body has an average thickness of not less than about 1.0millimeters.
 8. The carrier of claim 5 wherein the shrink-fittedmonolithic body has an average thickness of not greater than about 100millimeters.
 9. The carrier of claim 1 wherein the shrink-fittedmonolithic body is polymerized divinylbenzene.
 10. The carrier of claim1 wherein the at least a portion of the support is partially flattened.11. A system for testing a sample for the presence of a compound,comprising: a carrier including: a support; and a shrink-fittedmonolithic body attached to and surrounding at least a portion of thesupport; and a container including a cavity for holding a sample,wherein the shrink-fitted monolithic body sized to fit within the cavityand to be in contact with the sample.
 12. The system of claim 11 whereinthe support is a rod.
 13. The system of claim 11 wherein the support isa magnet or polymer coated magnet.
 14. The system of claim 11 whereinthe shrink-fitted monolithic body has an average thickness of not lessthan about 0.5 millimeters.
 15. (canceled)
 16. (canceled)
 17. The systemof claim 14 wherein the shrink-fitted monolithic body has an averagethickness of not greater than about 100 millimeters.
 18. The system ofclaim 11 wherein the shrink-fitted monolithic body conforms to the shapeof the cavity. 19.-30. (canceled)
 31. A method of determining thepresence of a compound in a solution comprises: adding the solution to acontainer; inserting a carrier into the container, the carrier includinga support and a shrink-fitted monolith adhered to the substrate, whereinthe shrink-fitted monolith is in contact with the solution; and i) whenthe shrink-fitted monolith adsorbs the compound: adsorbing the compoundto the shrink-fitted monolith; removing the shrink-fitted monolith fromthe solution in the container; providing the compound to a detector; anddetecting and/or quantifying the amount of the compound in the solutionbased on an output of the detector; or ii) when the monolith does notadsorb the compound; adsorbing interfering compounds to theshrink-fitted monolith; removing the shrink-fitted monolith from thesolution in the container; providing the solution to the detector; anddetecting and/or quantifying the amount of the compound in the solutionbased on an output of the detector. 32.-38. (canceled)
 39. The method ofclaim 31 wherein the detector includes a mass spectrometer.
 40. Themethod of claim 31 wherein the detector includes a liquid chromatographysystem.
 41. The method of claim 31 wherein the liquid chromatographysystem includes an optical detector, a flame ionization detector, or anycombination thereof.
 42. The method of claim 39 wherein the opticaldetector includes a UV detector, an IR detector, a visible lightdetector, a Raman detector, or any combination thereof.
 43. The methodof claim 31 wherein the detector includes a scintillation counter, anX-ray fluorescence detector, or any combination thereof.
 44. The methodof claim 31 wherein the detector includes a charged aerosol detector, aflame ionization detector, an aerosol-based detector, a flamephotometric detector, an atomic-emission detector, a nitrogen phosphorusdetector, an evaporative light scattering detector, an electrolyticconductivity detector, a MIRA detector, or any combination thereof. 45.The method of claim 31 wherein providing the compound to the detectorincludes removing the compound from the shrink-fitted monolith to thedetector.
 46. The method of claim 45 wherein removing the compound fromthe shrink-fitted monolith to the detector includes eluting the compoundinto a solution and providing the solution to the detector.
 47. Themethod of claim 31 wherein providing the compound to the detectorincludes providing the carrier and the adhered compound to the detector.48. The method of claim 31 wherein providing the compound to thedetector includes transferring the adhered compound from the carrierinto the detector.